Observability of paramagnetic NMR signals at over 10 000 ppm chemical shifts

Lutz Gade, Jonas C. Ott, Elizaveta A. Suturina, Ilya Kuprov, Joscha Nehrkorn, Alexander Schnegg, Markus Enders

Research output: Contribution to journalArticlepeer-review

Abstract

We report an experimental observation of 31 P NMR resonances shifted by over 10 000 ppm (meaning percent range, and a new record for solutions), and similar 1 H chemical shifts, in an intermediate-spin square planar ferrous complex [ t Bu (PNP)Fe–H], where PNP is a carbazole based pincer ligand. Using a combination of electronic structure theory, nuclear magnetic resonance, magnetometry, and terahertz electron paramagnetic resonance, the influence of magnetic anisotropy and zero-field splitting on the paramagnetic shift and relaxation enhancement is investigated. Detailed spin dynamics simulations indicate that, even with relatively slow electron spin relaxation ( T 1 ~ 10 -11 s), it remains possible to observe NMR signals of directly metal-bonded atoms because pronounced rhombicity in the electron zero-field splitting reduces nuclear paramagnetic relaxation enhancement.
Original languageEnglish
JournalAngewandte Chemie
Early online date5 Aug 2021
DOIs
Publication statusE-pub ahead of print - 5 Aug 2021

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